JP2017217758A - Filament material for three-dimensional molding and manufacturing method thereof, filament material set for three-dimensional molding and manufacturing method of three-dimensional molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a filament material for three-dimensional molding capable of reducing an influence of moisture absorption and preventing deterioration of molding stability or shape precision due to the moisture absorption, in use or in storage of the filament material for three-dimensional molding.SOLUTION: A filament material for three-dimensional molding includes a thermoplastic resin and desiccant particles. The number of desiccant particles not exposed on a surface of the filament material for three-dimensional molding is larger than the number of desiccant particles exposed on the surface of the filament material for three-dimensional molding.SELECTED DRAWING: None

Description

  The present invention relates to a three-dimensional modeling filament material and a manufacturing method thereof, a three-dimensional modeling filament material set, and a three-dimensional manufacturing method.

  Among three-dimensional modeling technologies, the fusion fusion modeling method (FDM (registered trademark)) is relatively inexpensive and can be modeled using the same material as the actual product, so its application range is wide. The principle of the hot-melt laminating method is that a filament material made of a thermoplastic resin is melted by heat to be semi-liquefied, then discharged from a head nozzle to a predetermined position based on 3D data, and then repeatedly laminated. This is a method of three-dimensional modeling and is simpler than other methods.

  Filament materials used in the hot melt lamination method are classified into model materials made of resin that are actually used for three-dimensional objects and support materials that are used for the purpose of supporting the model during modeling and removed after modeling. . In the absence of the support material, the shape and design that can be formed are greatly limited, and therefore it is preferable to use the support material in combination.

  Since the moisture content of these three-dimensional modeling filament materials greatly affects modeling stability and modeling accuracy, it is necessary to appropriately manage the temperature and humidity during storage and modeling.

  As a method for preventing moisture absorption of the filament material for three-dimensional modeling, for example, a cassette for containing a filament material, a drying chamber containing a rotatable spool and a desiccant, and a filament path connected to an outlet orifice extending from the chamber And a filament cassette provided with means for sending filaments from the spool and means for preventing air flow into the chamber (see, for example, Patent Document 1).

  It is an object of the present invention to provide a three-dimensional modeling filament material that reduces the influence of moisture absorption during use or storage of the three-dimensional modeling filament material, and suppresses the modeling stability and modeling accuracy associated with moisture absorption. To do.

The filament material for three-dimensional modeling of the present invention as a means for solving the above problems is a filament material for three-dimensional modeling that contains a thermoplastic resin and desiccant particles,
The number of the desiccant particles not exposed on the surface of the three-dimensional modeling filament material is larger than the number of the desiccant particles exposed on the surface of the three-dimensional modeling filament material.

  According to the present invention, it is possible to provide a three-dimensional modeling filament material that reduces the effects of moisture absorption during use or storage of the three-dimensional modeling filament material, and suppresses the modeling stability and modeling accuracy associated with moisture absorption. .

FIG. 1 is a schematic view showing an example of a state in which desiccant particles are exposed on the surface of the filament material. FIG. 2 is a schematic view showing an example of a state in which desiccant particles are not exposed on the surface of the filament material. FIG. 3 is a schematic diagram illustrating an example of an extrusion molding process and an extrusion molding apparatus. FIG. 4 is a schematic view showing an example of a coextrusion molding method. FIG. 5A is a plan view illustrating an example of a three-dimensional object formed using the three-dimensional object material of the present invention. FIG. 5B is a cross-sectional view taken along the line AA of the three-dimensional structure in FIG. 5A. FIG. 5C is a schematic cross-sectional view illustrating an example of a step of removing the support of the three-dimensional structure illustrated in FIG. 5B.

(Fill material for three-dimensional modeling)
The filament material for three-dimensional modeling of the present invention is a filament material for three-dimensional modeling containing a thermoplastic resin and desiccant particles,
The number of the desiccant particles not exposed on the surface of the three-dimensional modeling filament material is larger than the number of the desiccant particles exposed on the surface of the three-dimensional modeling filament material, and further necessary Depending on the situation, other components are contained.

  The filament material for three-dimensional modeling is a material used when a three-dimensional model is manufactured by a hot melt lamination method (FDM). The “filament” is formed by, for example, extruding a resin composition into a string shape or a thread shape. It means a material and may be referred to as “strand”.

  The method for preventing moisture absorption of the cassette for placing the three-dimensional modeling filament material of the prior art is an effective means for suppressing the moisture absorption of the three-dimensional modeling filament material. However, there is a limit to increasing the airtightness of the cassette, and only a life-prolonging effect can be obtained. Another problem is that the cost of the cassette increases. In particular, in order to maintain the hermeticity of the cassette, it is necessary to avoid the insertion and removal of the three-dimensional modeling filament material from the cassette as much as possible, and when the cassette is prepared for each three-dimensional modeling filament material, a widely accepted method It is based on the knowledge that it is not.

The three-dimensional modeling filament material has a two-layer configuration of a core part and a shell part,
The core portion is formed of a resin composition containing the thermoplastic resin and the desiccant particles,
It is preferable that the shell part is formed of a resin composition in which the amount of the desiccant particles is smaller than that of the core part.
The three-dimensional modeling filament material having a two-layer configuration of the core part and the shell part is preferably manufactured by coextrusion molding to be described later.

<Thermoplastic resin>
The filament material for three-dimensional modeling of the present invention contains a thermoplastic resin.
The thermoplastic resin refers to a resin that softens at a certain temperature or higher when heated, changes from solid to liquid, solidifies when cooled, and changes from liquid to solid.
The thermoplastic resin is not particularly limited as long as it has thermoplasticity, and any conventionally known resin can be used.
The thermoplastic resins can be broadly classified into two types, water-insoluble and water-soluble, and both can be used effectively. In the present invention, it is preferable to use the former water-insoluble resin as a model material and the latter water-soluble resin as a support material. Thereby, only the support material is dissolved and removed by a simple method of immersing the three-dimensional modeled object modeled using the model material and the support material in cold water or warm water, and a three-dimensional modeled object made of the model material is obtained. Is possible.

-Water-insoluble thermoplastic resin-
There is no restriction | limiting in particular as said water-insoluble thermoplastic resin, A conventionally well-known general purpose plastic, an engineer plastic, a super engineer plastic etc. are mentioned.
Examples of the general-purpose plastic include polylactic acid (PLA) resin, acrylonitrile-butadiene-styrene (ABS) resin, polystyrene (PS) resin, polyvinyl chloride (PVC) resin, acrylic (PMMA) resin, and polyethylene (PE) resin. And polypropylene (PP) resin.
Examples of the engineer plastic include polycarbonate (PC) resin, polyamide (PA) resin, modified polyphenylene ether (m-PPE) resin, polyester resin such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), and polyacetal (POM). ) Resins.
Examples of the super engineer plastic include polysulfone (PSU) resin, polyarylate (PAR) resin, polyetherimide (PEI), polyphenylene sulfide (PPS) resin, polyethersulfone (PES) resin, and polyamideimide (PAI) resin. , Polyether ether ketone (PEEK) resin, liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE) resin, polyvinylidene fluoride (PVDF), and the like.
The said water-insoluble thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.
As said water-insoluble thermoplastic resin, what was synthesize | combined suitably may be used and a commercial item may be used.

A thermoplastic elastomer having thermoplasticity can also be used. The thermoplastic elastomer is softened by heating and exhibits fluidity, but also has a property of returning to a rubber shape when cooled. By using these as a model material, a soft model is formed. be able to. The thermoplastic elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polystyrene-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, Examples thereof include polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polybutadiene-based thermoplastic elastomers.
These may be homopolymers (homopolymers), heteropolymers (copolymers), may be modified, or may be introduced with known functional groups. . In addition, a polymer alloy obtained by mixing these resins can be used effectively because the resin can be modified.

-Water-soluble thermoplastic resin-
As the water-soluble thermoplastic resin, not only a thermoplastic resin that is soluble in water, but also a thermoplastic resin that can be decomposed or disintegrated without being dissolved in water can be used effectively. The resin showing the solubility is a resin that is completely dissolved by water, whereas the resin showing the decomposability or disintegration is not completely dissolved even if a part of the resin is dissolved, The resin is in a state where the resin is finely decomposed and becomes unable to maintain the shape and properties originally possessed. The former water-soluble resin has a tendency to take time to completely dissolve, and the removal time of the support material may increase slightly, but the solution is transparent, and most of the residue remains after removal. There is no effect on the finish. On the other hand, in the case of the latter water-decomposable or disintegrating resin, when the support material is removed, the solution is opaque and insoluble matter remains, and the finish may be slightly inferior, but it is very difficult to shorten the removal time. It is effective for.
As a support material having both water-solubility and water-disintegrating property, a clean finish and a short removal time, there is a method using a water-soluble resin and adding an additive that promotes disintegration or decomposition, which is effective. As described above, all the thermoplastic resins which are dissolved by being attached to water, decomposed or disintegrated, or softened so as to be easily removed can be used effectively in the present invention.

Examples of the water-soluble thermoplastic resin include resins having hydrophilic substituents and structural units. Examples thereof include polyvinyl alcohol resins, vinyl acetate resins, polyalkylene oxides such as polyethylene oxide and polypropylene oxide, and polyacrylic acid. Examples thereof include a polymer, a polyvinyl pyrrolidone resin, a polyvinyl acetal resin, a water-soluble polyamide resin, a water-soluble polyester resin, cellulose, starch, and gelatin. These may be homopolymers (homopolymers), heteropolymers (copolymers), may be modified, or may be introduced with known functional groups. Further, it may be in the form of a salt. However, when used as a support material, among these water-soluble resins, from the viewpoint of shortening the removal time, resins having high water solubility are preferable, polyvinyl alcohol resins and polyalkylene oxides are preferable, and polyvinyl alcohol resins are particularly preferable.
The said water-soluble thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.
As said water-soluble thermoplastic resin, what was synthesize | combined suitably may be used and a commercial item may be used.

The weight average molecular weight of the thermoplastic resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50,000 or more and 1,000,000 or less, more preferably 75,000 or more and 500,000 or less. Preferably, 100,000 or more and 400,000 or less are more preferable. When the weight average molecular weight is within the above range, the ejection stability from the nozzles tends to increase, and the quality and accuracy of the resulting three-dimensional structure increase.
The weight average molecular weight can be measured using, for example, gel permeation chromatography (GPC).

<Drying agent particles>
The desiccant particles are particles having a water absorption function and may be referred to as a moisture absorbent or a water absorbent.
Since the filament material for three-dimensional modeling of the present invention contains the desiccant particles together with the thermoplastic resin, even if the resin absorbs moisture, the moisture is transferred to the desiccant particles, thereby reducing the moisture content of the resin. Since it is possible, it becomes possible to suppress the influence of the modeling stability, the modeling precision fall, etc. by the moisture absorption of the said filament material.

The desiccant particles are not particularly limited, and any conventionally known particulate desiccant can be used. The desiccant is classified into a physical adsorption desiccant and a chemical adsorption desiccant. The former physical adsorption desiccant is a desiccant that physically adsorbs moisture. For example, the surface of the desiccant has numerous molecular pores and gaps, and has a very large surface area. The function as a desiccant can be obtained by adsorbing moisture in the pores and gaps.
Examples of the physical adsorption desiccant include zeolite (molecular sieve), aluminosilicates such as allophane, silica gel, aluminum oxide, activated carbon, clay (clay). These may be used individually by 1 type and may use 2 or more types together.

The chemical adsorption desiccant is a desiccant that chemically adsorbs moisture. For example, the desiccant itself chemically reacts with water or forms a hydrate to obtain a function as a desiccant. It is what
Examples of the chemisorption desiccant include quick lime (calcium oxide), calcium chloride, magnesium sulfate, barium oxide, phosphorus pentoxide, potassium hydroxide, sodium hydroxide, potassium bromide, calcium bromide, copper sulfate, and chloride. Examples include zinc, calcium sulfate, and magnesium oxide. These may be used individually by 1 type and may use 2 or more types together.

Among these, it is preferable to use the physical adsorption type desiccant particles as the desiccant particles. The chemical adsorption desiccant particles include those having deliquescent properties such as calcium chloride and those causing volume expansion due to moisture absorption such as calcium oxide. When these are used as a three-dimensional modeling filament material, the filament may not be transported or nozzle clogging may occur, which is not preferable. On the other hand, the physical adsorption desiccant physically captures moisture, and therefore does not cause volume expansion due to deliquescence or moisture absorption, and has little effect on three-dimensional modeling. Moreover, since drying agent can be dehumidified when it heat-drys, it can be used repeatedly. Furthermore, since it has a moisture-releasing property depending on the use environment, it is also possible to prevent filament breakage due to excessive drying.
From the above, in the present invention, the physical adsorption desiccant is preferably used. However, even if it is a chemical adsorption type desiccant, what suppressed deliquescence and volume expansion is marketed, and these can be used effectively in the present invention.

  Since the effect of the desiccant particles is obtained by absorbing the moisture of the moisture-absorbed resin, in addition to the desiccant, a polymer material (water-absorbing resin) having water absorption can also be used effectively. Examples of the water-absorbing resin include a hydrophilic cross-linked polymer obtained by cross-linking a water-soluble polymer, and fine particles made of a water-absorbing polymer having a function of absorbing water and gelling to retain water. For example, polyacrylate, polysulfonate, maleic anhydride, polyacrylamide, polyvinyl alcohol, polyethylene oxide and other synthetic polymers, polyaspartate, polyglutamate, polyalginate , Starch-based, cellulose-based and other natural products. Furthermore, acrylic resin fine particles mainly composed of polymethyl methacrylate, polyacrylonitrile or the like are also effectively used. The water-absorbent resin is more preferably resin fine particles that have a high water-absorbing ability but may expand in volume and do not change greatly in volume even when absorbed. In that respect, among the acrylic resin fine particles, those in which the volume of the particles hardly changes even when moisture is absorbed or released are commercially available. Specific examples include hygroscopic fine particle tuftic HU series (manufactured by Toyobo Co., Ltd.), which can be used effectively in the present invention.

Of the above, zeolite is preferably used as the physical adsorption desiccant. The zeolite is a kind of aluminosilicate and has a network structure of silicon (Si), aluminum (Al), and oxygen (O). It has a very fine and uniform pore diameter of about 0.2 nm to 1 nm, and has a very high adsorption capacity. In addition, it can function only as a molecular sieve because it can adsorb only a substance that can pass through the pores. There are natural and artificial zeolites, and artificially synthesized zeolites are commercially available as molecular sieves and can be used particularly effectively in the present invention.
As the molecular sieve, those having a pore diameter of 0.3 nm (molecular sieve 3A), 0.4 nm (molecular sieve 4A), 0.5 nm (molecular sieve 5A), 1 nm (molecular sieve 13X) are known. You can choose from. In the present invention, since water is intended for adsorption, any of them can be used, but molecular sieve 3A or 4A is preferably selected.

In the three-dimensional modeling filament material of the present invention, the number of desiccant particles not exposed on the surface of the three-dimensional modeling filament material is greater than the number of desiccant particles exposed on the surface of the three-dimensional modeling filament material. It is characterized by. This is because when most of the desiccant particles are exposed on the surface of the filament material for three-dimensional modeling, the desiccant particles directly absorb moisture in the air, and the effect of the present invention is halved.
A conventionally known desiccant kneaded resin composition is intended to absorb moisture in the air. For example, Japanese Patent Application Laid-Open No. 2002-206046 discloses a film in which molecular sieves are kneaded, and is used for the purpose of drying air in a packaging container formed of the film. However, the three-dimensional modeling filament material of the present invention is intended to dry the three-dimensional modeling filament material itself, rather than drying the air inside like a packaging container. Therefore, it is not preferable that the desiccant is exposed on the surface of the three-dimensional modeling filament material. In the present invention, a higher effect can be obtained by increasing the number of desiccant particles not exposed on the surface of the three-dimensional modeling filament material than the number of desiccant particles exposed on the surface of the three-dimensional modeling filament material. It is done. Furthermore, the smaller the number of desiccant particles exposed on the surface of the three-dimensional modeling filament material, the better. It is particularly preferable that there are no exposed desiccant particles.

The state in which the desiccant particles are exposed on the surface of the three-dimensional modeling filament material is a state in which the desiccant particles are in contact with outside air, and the desiccant particles are in contact with outside air. Even if it is the state which protruded from the filament material surface for three-dimensional model | molding, it is contained even if it is a depressed state. For example, if the surface of the desiccant particles is covered with a resin, it is determined that the surface is not exposed regardless of the thickness of the resin. As an example, FIG. 1 is a schematic diagram showing a state in which the desiccant particles 2 are exposed from the surface of the three-dimensional modeling filament material 1, and FIG. 2 shows the desiccant particles 2 exposed from the surface of the three-dimensional modeling filament material 1. A schematic diagram showing the absence of this condition is described.
Further, as a method of obtaining the number of the desiccant particles exposed on the surface of the three-dimensional modeling filament material and the number not exposed, the surface or cross section of the three-dimensional modeling filament material can be obtained by using a scanning electron microscope (SEM) or a microscope. Etc., and can be obtained by counting the number of each desiccant particle per unit area. For example, the cross-sectional observation can be performed in the axial direction at any of a plurality of locations of the three-dimensional modeling filament material, and after calculating the number exposed on the surface and the number not exposed, the average value can be calculated. Alternatively, after performing surface observation of the three-dimensional modeling filament material and counting the number of exposures per unit area, cross-sectional observation is performed in the length direction at any plurality of locations of the three-dimensional modeling filament material, and exposure per unit area It can be obtained by counting the number that is not done and calculating the average value.

In the present invention, the minimum axial length of the desiccant particles is preferably 1 μm or more. Here, the minimum axial length refers to the length of the shortest axis of the desiccant particles. When the minimum axial length of the desiccant particles is 1 μm or more, a sufficient water absorption effect can be obtained.
The average particle diameter of the desiccant particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably in the range of 1 μm or more and 200 μm or less including the average primary particles and the average secondary particles. Specifically, the average primary particle of the desiccant particles is preferably 5 μm or more and 100 μm or less, and the average secondary particle diameter of the desiccant particles is preferably 5 μm or more and 200 μm or less. The desiccant particles are present not only as primary particles but also as secondary particles. In particular, the secondary particles are an aggregate of innumerable primary particles, and the water adsorbing ability is enhanced by forming a porous structure in which the gaps between the primary particles become pores. In this case, the smaller primary particles and the larger secondary particles are advantageous in increasing the adsorption capacity. From the above, as the desiccant particles, not only primary particles but also secondary particles can be used effectively. When the average particle diameter of the desiccant particles is within the above range, drying in the three-dimensional modeling filament material can be performed uniformly and efficiently, and the influence on the mechanical properties of the three-dimensional modeling filament material is small. This is preferable in that the influence of foaming is small.
The minimum axial length of the desiccant particles can be determined by a method for observing the shape such as a transmission electron microscope, a scanning electron microscope, or a microscope. Further, the average particle diameter can be measured using a particle size distribution measuring device or the like in addition to the above-mentioned electron microscope and microscope.

  The content of the desiccant particles is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 1% by mass or more and 70% by mass or less based on the total amount of the three-dimensional modeling filament material, 5 mass% or more and 50 mass% or less are more preferable, and 10 mass% or more and 40 mass% or less are still more preferable. When the content of the desiccant particles is within the above range, filament forming can be stably performed, and an effect of preventing defects due to moisture absorption of the filament material for three-dimensional modeling can be obtained, and stability during modeling It is preferable in that it has little influence on the quality and accuracy of the molded object. However, the content of the desiccant particles varies depending on the moisture absorption capacity, the average single particle diameter, the dispersion state, and the like of the desiccant particles, and therefore is appropriately determined in consideration of effects and side effects.

<Other ingredients>
The filament material for three-dimensional modeling of the present invention can contain other components in addition to the thermoplastic resin and the desiccant particles, and is useful.
Examples of the other components include plasticizers, fillers, reinforcing agents, stabilizers, dispersants, antioxidants, flame retardants, foaming agents, antistatic agents, lubricants, colorants, pigments, and various polymer modifications. Agents and the like. By adding these, improvement of filament forming stability by improving fluidity, improvement of dimensional accuracy of filament material for 3D modeling, improvement of mechanical properties of filament material for 3D modeling, prevention of deterioration of filament material for 3D modeling, Furthermore, it is very effective since the effects of improving the modeling stability by a three-dimensional (3D) printer and the quality and accuracy of the three-dimensional model to be obtained can be obtained.

(3D modeling filament material set)
The filament material set for three-dimensional modeling of the present invention is a filament material for three-dimensional modeling of the present invention in which the thermoplastic resin is water-insoluble,
The three-dimensional modeling filament material of the present invention in which the thermoplastic resin is water-soluble, and further includes other materials as necessary.
The three-dimensional modeling filament material of the present invention in which the thermoplastic resin is water-insoluble is preferably used as a model material, and the three-dimensional modeling filament material of the present invention in which the thermoplastic resin is water-soluble is used as a support material. Thereby, only the support material is dissolved and removed by a simple method of immersing the three-dimensional modeled object modeled using the model material and the support material in cold water or warm water, and a three-dimensional modeled object made of the model material is obtained. Is possible.

(Manufacturing method of filament material for three-dimensional modeling)
The filament material for three-dimensional modeling of the present invention can be manufactured using a conventionally known extrusion molding method.
Here, the schematic diagram of the general process of extrusion molding is shown in FIG.
For example, a resin composition containing the thermoplastic resin and the desiccant particles or other components is put through a hopper 203 and extruded while being melt kneaded by a screw 204 in a cylinder (also referred to as a barrel) of an extruder 201. The filaments are formed by passing a mold 202 selected to have a filament diameter of. Then, it solidifies by cooling with the cooler 210, takes up with the take-up machine 220, winds up with the wind-up machine 230, and cuts with the cutting machine to produce the three-dimensional modeling filament material of the present invention. can do. In addition, you may comprise a winder and a cutting machine integrally.

The extruder 201 is generally a screw type. In addition to the single screw extruder, the screw type includes a multi-screw extruder having two or more screws or a special extruder.
The single-screw extruder is an extruder having a single screw mounted on a cylinder, and includes, for example, a driving device such as a hopper and a motor, a speed reducer, a screw, a cylinder, a heater, a blower, and a temperature control device. Yes. Mold is attached to the tip of the cylinder.
The biaxial (multi-axial) extruder is an extruder equipped with two or more screws in a cylinder. In general, two-screw type is mainly used, the two shafts are parallel, the shafts are obliquely crossed, and the screw flight engagement type and non-engagement type, the screw rotation direction is the same direction There are things in different directions.
The special extruder is classified into three types: a combination of two types of extruders in two stages, a screw and barrel having a special shape, and a non-screw type.
Examples of the method for melt-kneading the resin composition include a method of melt-kneading for each batch using a kneader, a mixer, or the like, in addition to using the extruder.

  The cooler 210 is a device that cools and solidifies the extruded filament, and is an important process in determining the size and quality of the filament. Generally, it is largely divided into water cooling and air cooling, and means such as a water tank, a water shower, a cooling roll, and a cooling board are used. The water-insoluble filament material of the present invention can be water-cooled, but the water-soluble filament material is air-cooled.

The take-up machine 220 is a device for taking up the filament, but in order to maintain high dimensional accuracy and quality, an appropriate pulling force and a uniform pulling speed without pulsation are required.
The winder and cutter 230 is a device for winding and cutting the filament on a bobbin or the like.
In addition to the above steps, after cooling, it can be heated again and stretched, which may be effective in increasing strength.

  In the three-dimensional modeling filament material of the present invention, the number of desiccant particles not exposed on the surface of the three-dimensional modeling filament material is larger than the number of desiccant particles exposed on the surface of the three-dimensional modeling filament material. It is characterized by that. Although it is possible to manufacture using the above general extrusion molding method, a coextrusion molding method can be used as a method for controlling the distribution state of the desiccant particles in the filament material for three-dimensional modeling. ,It is valid.

In the manufacturing method of the three-dimensional modeling filament material of the present invention, the three-dimensional modeling filament material is
A resin composition containing the desiccant particles in the thermoplastic resin;
Using at least two selected from a resin composition in which the content of the desiccant particles is reduced, and a resin composition not containing the desiccant particles,
Manufactured using a coextrusion molding machine.

The co-extrusion molding is a method of performing molding by extruding different resin compositions from a plurality of extruders and laminating them.
FIG. 4 shows a schematic view of coextrusion molding. For example, in the resin composition 5 used for forming the core portion of the filament material for three-dimensional modeling and the resin composition 6 also used for forming the shell portion, the content of the desiccant particles is more resin composition than the resin composition 5. Adjustment is possible by reducing the number of objects 6. More specifically, for example, the content ratio of the thermoplastic resin and the desiccant particles is 5: 5 resin composition A, the same content ratio is 7: 3 resin composition B, and the same content ratio is When a resin composition C having a ratio of 9: 1 and a resin composition D having a similar ratio of 10: 0 are prepared, A is used for the resin composition 5 in the core portion, and C is used for the resin composition 6 in the shell portion. Can be made. In order to produce a three-dimensional modeling filament material in which the desiccant particles are not exposed on the surface, for example, it is possible by using B for the resin composition 5 in the core portion and D for the resin composition 6 in the shell portion. Become.
The diameter of the filament material for three-dimensional modeling of the present invention is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 0.5 mm or more and 10 mm or less, and 1.5 mm or more and 3.5 mm or less. Is more preferable.

(Manufacturing method and 3D modeling apparatus of 3D model)
The manufacturing method of the three-dimensional molded item of this invention is a manufacturing method of the three-dimensional molded item obtained by modeling the filament material for three-dimensional modeling of this invention using a conventionally well-known three-dimensional modeling apparatus. The three-dimensional modeling filament material may be a model material, a support material, or both.

  The three-dimensional modeling apparatus is, for example, a unit (nozzle head) that heats and melts the resin composition containing the thermoplastic resin and the desiccant particles based on input three-dimensional shape data and discharges the resin composition to an arbitrary position. ) And means (bed) for depositing the discharged resin composition, and other means as necessary. Specifically, a known hot melt lamination (FDM (registered trademark)) type three-dimensional modeling apparatus (3D printer) is preferably used. These three-dimensional modeling apparatuses convey the three-dimensional modeling filament material of the present invention toward the nozzle head at a predetermined speed, and in the nozzle head portion, the three-dimensional modeling filament material is heated and melted and discharged to an arbitrary position. Is done. The discharged three-dimensional modeling filament material is deposited on the bed. When these series of operations are completed, the bed is lowered, and by repeating the same operation, the three-dimensional modeling filament material discharged from the nozzle head is laminated, and a three-dimensional modeled object can be manufactured.

  The heating temperature of the nozzle head is not particularly limited as long as the three-dimensional modeling filament material can be melted, and can be appropriately selected according to the purpose. However, the thermoplastic resin contained in the three-dimensional modeling filament material is decomposed. It is preferred not to exceed the temperature. Exceeding the decomposition temperature of the thermoplastic resin causes nozzle clogging due to the decomposition product, leading to a decrease in modeling stability.

The bed can be effectively provided with heating means so that the three-dimensional modeling filament material does not peel off during modeling. The heating temperature is not particularly limited as long as the filament material for three-dimensional modeling does not peel off from the bed during modeling, or the three-dimensional model does not melt and deform on the bed, and can be appropriately selected according to the purpose, It is preferable that it is more than the glass transition temperature of the thermoplastic resin contained in the three-dimensional modeling filament material. In addition, a method of sticking a sheet, a sticker or the like for improving the adhesion with the three-dimensional modeling filament material on the bed is also effective. However, if the adhesiveness is too strong, it may be difficult to take out the three-dimensional model after the modeling is finished.
Since these three-dimensional modeling filament materials are for directly producing a three-dimensional modeled object, generally model materials made of water-insoluble thermoplastic resins are used, but support materials made of water-soluble thermoplastic resins are used. It is also possible to model.
On the other hand, the support material is originally used to support modeling by the model material. Therefore, when producing a three-dimensional modeled object, a three-dimensional model apparatus having at least two nozzle heads for a model material and a support material is usually used. Thus, after producing the three-dimensional molded item which consists of a model material and a support material, the three-dimensional molded item which consists of a model material can be obtained by removing only a support material.

The schematic which shows an example of the method of manufacturing a three-dimensional molded item using a support material to FIG. 5A to FIG. 5C is shown. FIG. 5A is a plan view illustrating an example of a three-dimensional modeled object modeled using the model material 20 and the support material 10. FIG. 5B is a cross-sectional view taken along the line AA of the three-dimensional structure in FIG. 5A. Since the handle portion in the figure cannot be clearly modeled by the method of stacking and modeling from below, the support material 10 is stacked in order to support the handle portion.
FIG. 5C is a schematic cross-sectional view showing an example of a process of removing the support material 10 from the three-dimensional structure shown in FIG. 5B. Since the support material 10 is made of a water-soluble thermoplastic resin, when the three-dimensional structure obtained in FIG. 5B is immersed in a container filled with cold water or warm water, only the support material 10 is dissolved and removed. Thus, a three-dimensional modeled object modeled with the model material 20 can be easily obtained.
The above-mentioned form is a three-dimensional modeling filament material of the present invention including a water-soluble thermoplastic resin of the present invention including a water-insoluble thermoplastic resin as the model material 20 and a water-soluble thermoplastic resin of the support material 10. By using these in combination, it is possible to achieve improvement in modeling stability or modeling quality for both the model material and the support material. Therefore, in the present invention, these combinations are defined as a three-dimensional modeling filament material set.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

In the following examples and comparative examples, the minimum axial length and the average particle diameter of the desiccant particles were measured as follows.
<Minimum axial length and average particle diameter of desiccant particles>
The minimum axial length of the desiccant particles was measured by a shape observation method using a transmission electron microscope, a scanning electron microscope, or a microscope. The average particle size was measured using a transmission electron microscope, a scanning electron microscope, or a particle size distribution measuring device.

Example 1
-Production of filament material 1 for three-dimensional modeling-
70 parts by mass of polylactic acid resin (3001D, manufactured by Nature Works, D-form content 1.4%, melting point 165 ° C., weight average molecular weight 1860,000) as thermoplastic resin, synthetic zeolite (molecular sieve 3A) as desiccant particles , Powder, minimum axial length of 1 μm or more, average particle diameter of about 10 μm, Union Showa Co., Ltd.) 30 parts by mass is melt kneaded and filament molded using an extruder as shown in FIG. 3D modeling filament material 1 was produced.
In addition, as a result of performing cross-sectional SEM observation of the obtained three-dimensional modeling filament material 1 using a scanning electron microscope (ULTRA55, manufactured by ZEISS), the desiccant particles exposed on the surface are not exposed. It was confirmed that there were more desiccant particles.

(Example 2)
-Production of three-dimensional modeling filament material 2-
In Example 1, except that the desiccant particles were changed to synthetic zeolite (A-4, minimum axial length of 1 μm or more, average particle diameter of about 75 μm, manufactured by Tosoh Corporation), the diameter 1 A filament material 2 for three-dimensional modeling of .75 mm was produced.
In addition, as a result of performing cross-sectional SEM observation of the obtained filament material 2 for three-dimensional modeling similarly to Example 1, there are more desiccant particles which are not exposed than the desiccant particle which is exposed on the surface. It was confirmed.

(Example 3)
-Production of three-dimensional modeling filament material 3-
In Example 1, 60 parts by mass of a polylactic acid resin (3001D, D-form content: 1.4%, melting point: 165 ° C., weight average molecular weight: 186,000, manufactured by Nature Works) as a thermoplastic resin, and silica gel as a desiccant particle (Sunsphere H-201, minimum axial length of 1 μm or more, average particle diameter of about 20 μm, manufactured by AGC S-Tech Co., Ltd.) Similar to Example 1, except for using 40 parts by mass, for three-dimensional modeling with a diameter of 1.75 mm Filament material 3 was produced.
As a result of carrying out cross-sectional SEM observation of the obtained three-dimensional modeling filament material 3 in the same manner as in Example 1, it was confirmed that there were more unexposed desiccant particles than exposed desiccant particles on the surface. did.

Example 4
-Production of filament material 4 for three-dimensional modeling-
In Example 3, except that the desiccant particles were changed to silica gel (NIPGEL BY-001, minimum axial length of 1 μm or more, average particle diameter of about 14 μm, manufactured by Tosoh Silica Co., Ltd.), A filament material 4 for three-dimensional modeling having a diameter of 1.75 mm was produced.
As a result of conducting cross-sectional SEM observation of the obtained filament material 4 for three-dimensional modeling in the same manner as in Example 1, it was confirmed that there were more desiccant particles not exposed than the desiccant particles exposed on the surface. did.

(Example 5)
-Production of three-dimensional modeling filament material 5-
In Example 3, except that the desiccant particles were changed to acrylic resin fine particles (Tuffic HU-720P, minimum axial length of 1 μm or more, average particle diameter of about 50 μm, manufactured by Toyobo Co., Ltd.), in the same manner as in Example 3, A filament material 5 for three-dimensional modeling having a diameter of 1.75 mm was produced.
As a result of performing cross-sectional SEM observation of the obtained filament material 5 for three-dimensional modeling in the same manner as in Example 1, it was confirmed that there were more desiccant particles not exposed than the desiccant particles exposed on the surface. did.

(Example 6)
-Production of three-dimensional modeling filament material 6-
In Example 3, the thermoplastic resin was changed to polyvinyl alcohol resin (G polymer OKS-8164P, melting point 170 ° C., manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) in the same manner as in Example 3, and the diameter was 1.75 mm. The three-dimensional modeling filament material 6 was produced.
As a result of performing cross-sectional SEM observation of the obtained filament material for three-dimensional modeling in the same manner as in Example 1, it was confirmed that there were more desiccant particles not exposed than the desiccant particles exposed on the surface. did.

(Example 7)
-Preparation of filament material 7 for three-dimensional modeling-
In Example 3, except that the thermoplastic resin was changed to polyamide resin (6 nylon, Amilan CM1021FS, melting point 225 ° C., manufactured by Toray Industries, Inc.), in the same manner as in Example 3, for three-dimensional modeling with a diameter of 1.75 mm Filament material 7 was produced.
As a result of performing cross-sectional SEM observation of the obtained filament material 7 for three-dimensional modeling in the same manner as in Example 1, it was confirmed that there were more desiccant particles not exposed than the desiccant particles exposed on the surface. did.

(Example 8)
-Production of filament material 8 for three-dimensional modeling-
As a resin composition for the core part, 65 parts by mass of a polylactic acid resin (3001D, manufactured by Nature Works, D-form content 1.4%, melting point 165 ° C., weight average molecular weight 1860,000) as a thermoplastic resin, desiccant 35 parts by mass of synthetic zeolite (molecular sieve 3A, powder, minimum axial length of 1 μm or more, average particle diameter of about 10 μm, manufactured by Union Showa Co., Ltd.) as particles as a resin composition for the shell part, and a polylactic acid resin ( 3001D, manufactured by Nature Works, D-form content: 1.4%, melting point: 165 ° C., weight average molecular weight: 186,000, 90 parts by mass, synthetic zeolite (molecular sieve 3A, powder, minimum axial length of 1 μm or more) as desiccant particles 10 parts by mass of an average particle size of about 10 μm, manufactured by Union Showa Co., Ltd.) was melt kneaded using a coextrusion molding machine as shown in FIG. It performed Iramento molding, to produce a three-dimensional article filament material 8 having a diameter of 1.75 mm.
As a result of performing cross-sectional SEM observation of the obtained filament material 8 for three-dimensional modeling in the same manner as in Example 1, it was confirmed that there were more unexposed desiccant particles than the desiccant particles exposed on the surface. did.

Example 9
-Production of three-dimensional modeling filament material 9-
As a resin composition for the core part, a thermoplastic resin and a polyvinyl alcohol resin (G polymer OKS-8150P, melting point 170 ° C., manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 50 parts by mass, as a desiccant particle, synthetic zeolite (Molecular Sieve 3A, 50 parts by mass of powder, minimum axial length of 1 μm or more, average particle diameter of about 10 μm, manufactured by Union Showa Co., Ltd., as a resin composition for shell, polyvinyl alcohol resin (G polymer OKS-8150P, melting point 170 ° C.) as a thermoplastic resin 100 parts by mass (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was melt-kneaded and filament-molded using a coextrusion molding machine as shown in FIG. 4 to produce a filament material 9 for three-dimensional modeling having a diameter of 1.75 mm.
As a result of carrying out cross-sectional SEM observation of the obtained filament material 9 for three-dimensional modeling similarly to Example 1, the desiccant particle exposed on the surface was not recognized.

(Example 10)
-Production of three-dimensional modeling filament material 10-
As a resin composition for the core part, a thermoplastic resin and a polyamide resin (6 nylon, Amilan CM1021FS, melting point 225 ° C., manufactured by Toray Industries, Inc.) 70 parts by mass, a desiccant particle, a synthetic zeolite (molecular sieve 3A, powder, minimum axis) 30 parts by mass of 1 μm or more in length, average particle diameter of about 10 μm, manufactured by Union Showa Co., Ltd., as a resin composition for the shell portion, a thermoplastic resin, polyamide resin (6 nylon, Amilan CM1021FS, melting point 225 ° C., manufactured by Toray Industries, Inc. ) 100 parts by mass were melt-kneaded and filament-molded using a coextrusion molding machine as shown in FIG. 4 to produce a three-dimensional modeling filament material 10 having a diameter of 1.75 mm.
As a result of carrying out cross-sectional SEM observation of the obtained three-dimensional modeling filament material 10 in the same manner as in Example 1, no desiccant particles exposed on the surface were observed.

(Example 11)
-Production of three-dimensional modeling filament material 11-
Example 10 is the same as Example 10 except that the desiccant particles of the core portion resin composition were changed to activated alumina (minimum axial length of 1 μm or more, average particle diameter of about 75 μm, manufactured by Wako Pure Chemical Industries, Ltd.). Similarly, a filament material 11 for three-dimensional modeling having a diameter of 1.75 mm was produced.
As a result of performing cross-sectional SEM observation of the obtained three-dimensional modeling filament material 11 in the same manner as in Example 1, no desiccant particles exposed on the surface were observed.

(Example 12)
-Production of filament material 12 for three-dimensional modeling-
In Example 10, the desiccant particles of the core part resin composition were changed to calcium oxide (minimum axial length of 1 μm or more, average particle diameter of about 30 μm) in the same manner as in Example 10 except that the diameter was 1.75 mm. The three-dimensional modeling filament material 12 was produced.
As a result of carrying out cross-sectional SEM observation of the obtained three-dimensional modeling filament material 12 in the same manner as in Example 1, no desiccant particles exposed on the surface were observed.

(Example 13)
-Production of three-dimensional modeling filament material 13-
In Example 6, the three-dimensional modeling filament material 13 having a diameter of 1.75 mm was obtained in the same manner as in Example 6 except that nanoclay (montmorillonite, minimum axial length of less than 1 μm, average particle diameter of 1 μm) was used as the desiccant particles. Produced.
As a result of carrying out cross-sectional SEM observation of the obtained filament material for three-dimensional modeling in the same manner as in Example 1, it was confirmed that there were more desiccant particles not exposed than desiccant particles exposed on the surface. did.

(Comparative Example 1)
-Production of three-dimensional modeling filament material 14-
In Example 1, a three-dimensional modeling filament material 14 having a diameter of 1.75 mm was produced in the same manner as in Example 1 except that it did not contain desiccant particles.

(Comparative Example 2)
-Production of three-dimensional modeling filament material 15-
As a resin composition for a core part, a polyvinyl alcohol resin (G polymer OKS-8150P, melting point 170 ° C., manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 100 parts by mass as a thermoplastic resin, and as a resin composition for a shell part, a polyvinyl alcohol resin ( G polymer OKS-8150P, melting point 170 ° C., Nippon Synthetic Chemical Industry Co., Ltd. 50 parts by mass, as desiccant particles, synthetic zeolite (molecular sieve 3A, powder, minimum axial length 1 μm or more, average particle diameter of about 10 μm, Union Showa 50 parts by mass) were melt-kneaded and filament-molded using a coextrusion molding machine as shown in FIG. 4 to produce a solid material filament material 15 having a diameter of 1.75 mm.
As a result of carrying out cross-sectional SEM observation of the obtained three-dimensional modeling filament material 15 in the same manner as in Example 1, it was confirmed that there were fewer unexposed desiccant particles than exposed desiccant particles on the surface. did.

  Next, various characteristics of the three-dimensional modeling filament materials 1 to 15 of Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.

<Modeling stability>
Each of the produced three-dimensional modeling filament materials was stored at 30 ° C. in an environment of 50% RH for 7 days, and then a three-dimensional model was manufactured using a hot-melt type three-dimensional modeling apparatus. The nozzle temperature was 35 ° C. higher than the melting point of the thermoplastic resin. The bed temperature was set between 45 ° C and 100 ° C. The modeling speed was 60 mm / sec.
About modeling stability, it was determined whether modeling stopped on the way by the conveyance failure of a filament during modeling, discharge failure, peeling from a bed, etc., and modeling stability was evaluated according to the following reference | standard.
[Evaluation criteria]
◎: The three-dimensional model was completed without stopping the modeling from the beginning to the end. ○: The modeling was stopped several times, but it could be revived and the three-dimensional model was completed. △: Modeling was 50% After the above progress, the modeling stopped frequently, and the three-dimensional model was not completed. ×: The modeling stopped frequently from the initial stage of modeling, and the modeling did not reach 10%.

<Modeling quality>
Modeling quality evaluation was performed about the three-dimensional molded item completed by the said modeling stability evaluation. The modeling quality was evaluated by visually observing the obtained three-dimensional modeled object and the presence or absence of defects and dimensional accuracy. Regarding the defects, the presence or absence of voids, the presence or absence of protrusions or stringing, the presence or absence of warpage, the presence or absence of peeling between pitches were determined, and the molding quality was evaluated according to the following criteria.
[Evaluation criteria]
◎: No conspicuous defects were found in the three-dimensional modeled object, and the target three-dimensional modeled object was obtained. ○: Several inconspicuous small defects were found, but it can be determined that there is no problem. ○ ~ △: Many inconspicuous small defects were found. However, it can be judged that there is no problem. △: There are many conspicuous defects and it is clear that the quality is clearly low.

(Example 14)
The three-dimensional modeling filament material of Example 1 is used as a model material, the three-dimensional modeling filament material of Example 6 is used as a support material, and the three-dimensional modeling object shown in FIG. Manufactured. The nozzle temperature was 35 ° C. higher than the melting point of the thermoplastic resin. The bed temperature was set to 70 ° C. The modeling speed was 60 mm / sec for the model material and 30 mm / sec for the support material.

(Example 15)
The three-dimensional modeling filament material of Example 10 is used as a model material, the three-dimensional modeling filament material of Example 9 is used as a support material, and the three-dimensional modeling object shown in FIG. Manufactured. The nozzle temperature was 35 ° C. higher than the melting point of the thermoplastic resin. The bed temperature was set to 80 ° C. The modeling speed was 60 mm / sec for the model material and 30 mm / sec for the support material.

  Next, the support material removal test was performed as follows about the three-dimensional molded item obtained by Examples 14-15. The results are shown in Table 2.

<Support material removal test>
Each three-dimensional model was immersed in a container containing 20 ° C. water, and stirred using a magnetic stirrer. After stirring for a predetermined time, the sample is taken out, dried at 50 ° C. for 24 hours, then the weight is measured, the residual amount on the sample with respect to the amount of support material used is measured, and the residual rate of the support material is obtained. It was. Evaluation was performed according to the following criteria. The results are shown in Table 2.
[Evaluation criteria]
◎: 1 hour after immersion, 5% or less support material remaining ○: 3 hours after immersion, 5% or less support material △: 5 hours after immersion The remaining rate of the support material is over 5%, and then the remaining rate of the support material is 5% or less by rinsing with a brush. ×: Even after 24 hours of immersion, the remaining rate of the support material is 50% or more

Aspects of the present invention are as follows, for example.
<1> A filament material for three-dimensional modeling containing a thermoplastic resin and desiccant particles,
Three-dimensional modeling characterized in that the number of desiccant particles not exposed on the surface of the three-dimensional modeling filament material is larger than the number of desiccant particles exposed on the surface of the three-dimensional modeling filament material. Filament material.
<2> The three-dimensional modeling filament material according to <1>, wherein the desiccant particles have a minimum axial length of 1 μm or more.
<3> The three-dimensional modeling filament material according to any one of <1> to <2>, wherein the desiccant particles are not exposed from the three-dimensional modeling filament material.
<4> The three-dimensional modeling filament material has a two-layer configuration of a core part and a shell part,
The core portion is formed of a resin composition containing the thermoplastic resin and the desiccant particles,
The filament material for three-dimensional modeling according to any one of <1> to <3>, wherein the shell portion is formed of a resin composition having a smaller amount of the desiccant particles than the core portion.
<5> The three-dimensional modeling filament material according to any one of <1> to <4>, wherein the desiccant particles are physical adsorption desiccant particles.
<6> The three-dimensional modeling filament material according to any one of <1> to <5>, wherein the desiccant particles are at least one selected from zeolite, silica gel, alumina, and a water absorbent resin.
<7> The filament material for three-dimensional modeling according to any one of <1> to <6>, wherein an average particle size of the desiccant particles is 1 μm or more and 200 μm or less including average primary particles and average secondary particles. It is.
<8> The three-dimensional modeling filament material according to any one of <1> to <7>, wherein the thermoplastic resin is water-insoluble;
The filament material for three-dimensional modeling according to any one of <1> to <7>, wherein the thermoplastic resin is water-soluble,
It is a filament material set for three-dimensional modeling characterized by having.
<9> The filament material for three-dimensional modeling is
A resin composition containing the desiccant particles in the thermoplastic resin;
Using at least two selected from a resin composition in which the content of the desiccant particles is reduced, and a resin composition not containing the desiccant particles,
The method for producing a filament material for three-dimensional modeling according to any one of <1> to <7>, wherein the filament material is produced using a coextrusion molding apparatus.
<10> A method for producing a three-dimensional structure including a step of heating and melting the filament material for three-dimensional structure according to any one of <1> to <7>, wherein the three-dimensional structure is manufactured. It is.
<11> Using the filament material for three-dimensional modeling, in which the thermoplastic resin is water-soluble, as a support material, and after forming a predetermined three-dimensional modeled object, the step <10> including a step of removing a portion made of the support material It is a manufacturing method of the three-dimensional molded item of description.

  The filament material for three-dimensional modeling according to any one of <1> to <7>, the filament material set for three-dimensional modeling according to <8>, the method for producing the filament material for three-dimensional modeling according to <9>, And according to the manufacturing method of the three-dimensional molded item according to any one of <10> to <11>, the problems in the related art can be solved and the object of the present invention can be achieved.

JP-T-2004-504177

DESCRIPTION OF SYMBOLS 1 Filament material for three-dimensional modeling 2 Desiccant particle 10 Support material 20 Model material

Claims (11)

A three-dimensional modeling filament material containing a thermoplastic resin and desiccant particles,
Three-dimensional modeling characterized in that the number of desiccant particles not exposed on the surface of the three-dimensional modeling filament material is larger than the number of desiccant particles exposed on the surface of the three-dimensional modeling filament material. Filament material.   The filament material for three-dimensional modeling according to claim 1, wherein a minimum axial length of the desiccant particles is 1 µm or more.   The filament material for three-dimensional modeling according to claim 1, wherein the desiccant particles are not exposed from the filament material for three-dimensional modeling. The three-dimensional modeling filament material has a two-layer configuration of a core part and a shell part,
The core portion is formed of a resin composition containing the thermoplastic resin and the desiccant particles,
The three-dimensional modeling filament material according to any one of claims 1 to 3, wherein the shell portion is formed of a resin composition having a smaller amount of the desiccant particles than the core portion.   The filament material for three-dimensional modeling according to any one of claims 1 to 4, wherein the desiccant particles are physical adsorption desiccant particles.   The filament material for three-dimensional modeling according to any one of claims 1 to 5, wherein the desiccant particles are at least one selected from zeolite, silica gel, alumina, and a water absorbent resin.   7. The filament material for three-dimensional modeling according to claim 1, wherein an average particle diameter of the desiccant particles is 1 μm or more and 200 μm or less including an average primary particle and an average secondary particle. The three-dimensional modeling filament material according to any one of claims 1 to 7, wherein the thermoplastic resin is water-insoluble.
The thermoplastic resin according to any one of claims 1 to 7, wherein the thermoplastic resin is water-soluble,
The filament material set for three-dimensional modeling characterized by having. The three-dimensional modeling filament material is
A resin composition containing the desiccant particles in the thermoplastic resin;
Using at least two selected from a resin composition in which the content of the desiccant particles is reduced, and a resin composition not containing the desiccant particles,
It manufactures using a coextrusion molding apparatus, The manufacturing method of the filament material for three-dimensional modeling in any one of Claim 1 to 7 characterized by the above-mentioned.   A method for manufacturing a three-dimensional structure, comprising a step of heating and melting the filament material for three-dimensional structure according to any one of claims 1 to 7, and manufacturing a three-dimensional structure. The three-dimensional model | molding of Claim 10 including the process of removing the part which consists of the said support material, after forming the predetermined three-dimensional model | molding object using the filament material for three-dimensional model | molding whose water-soluble thermoplastic resin is a support material. Manufacturing method.